4-Toluenesulfonyl chloride → Methyl 3-chloro-2-(methylsulfanyl)prop-2-enoate

HRID 2061023

反応式

HRID 2061023 の反応式
[H-].[Na+].[CH3:3][S:4][CH2:5][C:6]([O:8][CH3:9])=[O:7].[CH:10]([O:12][CH3:13])=[O:11].[C:14]1([CH3:24])[CH:19]=[CH:18][C:17]([S:20]([Cl:23])(=[O:22])=[O:21])=[CH:16][CH:15]=1>CN(C=O)C>[CH3:3][S:4][C:5](=[CH:13][O:12][S:20]([C:17]1[CH:18]=[CH:19][C:14]([CH3:24])=[CH:15][CH:16]=1)(=[O:22])=[O:21])[C:6]([O:8][CH3:9])=[O:7].[Cl:23][CH:6]=[C:5]([S:4][CH3:3])[C:10]([O:12][CH3:13])=[O:11]

参加物

7

反応物 4

HCID 73974-Toluenesulfonyl chlorideHCID 7865Methyl formateHCID 24758Sodium hydrideHCID 85522Methyl (methylthio)acetate

生成物 2

HCID 59498538Methyl 3-chloro-2-(methylsulfanyl)prop-2-enoateHCID 72308159Methyl 2-methylthio-3-(p-toluenesulfonyloxy)acrylate

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

To a suspension of 21.4 g (535 mmol) of sodium hydride (60% in oil) in 200 ml of DMF was added dropwise a mixture of 25.8 g (214 mmol) of methyl 2-(methylthio)acetate and 26.5 g (428 mmol) of methyl formate under ice cooling and stirred at room temperature overnight. To the reaction mixture was added portionwise 27.0 g (141 mmol) of p-toluenesulfonyl chloride under ice cooling and stirred at room temperature for 1 hour. After dilution with tert-butyl methyl ether, the solution was washed sequentially with water and saturated NaCl solution, dried over anhydrous MgSO4, and concentrated. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=5/1) to obtain 9.72 g of methyl 2-(methylthio)-3-(p-toluenesulfonyloxy)-2-propenoate and 1.88 g of methyl 3-chloro-2-(methylthio)-2-propenoate.

後処理

  1. additionwas added dropwise
  2. stirringstirred at room temperature for 1 hour
  3. washAfter dilution with tert-butyl methyl ether, the solution was washed sequentially with water and saturated NaCl solution
  4. dry with materialdried over anhydrous MgSO4
  5. concentrationconcentrated
  6. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=5/1)

出典と根拠

ORDレコード
ord-917a295a3c904fd19d4e3edda2058cc1
出典データセット
uspto-grants-2012_10
特許番号
US08278473B2

関連ノート

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